Azo dyes from an oxadiazolyl-substituted aniline

ABSTRACT

Compounds of the formula ##STR1## in which K is ##STR2## Ar 1  is phenyl; phenyl substituted by chlorine, methoxy, ethoxy, methyl, acetylamino or benzoylamino; or ##STR3## Ar 2  is phenyl; or phenyl substituted by chlorine, methyl or sulfamoyl, 
     T 1  is methyl or carbamoyl, 
     T 2  is cyano or carbamoyl, 
     Z is hydrogen, chlorine, bromine or trifluoromethyl, 
     Z 1  is hydrogen, chlorine, or bromine, and 
     R is phenyl; phenyl substituted by chlorine, bromine, hydroxy, methoxy, ethoxy, C 1  to C 4  alkyl, cyano, carbamoyl, nitro, phenyl, sulfamoyl, N-phenylsulfamoyl, acetylamino or benzoylamino; naphthyl; N-phenylphthalimidyl; or pyridyl. 
     These compounds are dyes having mostly pigmentary character and are eminently suitable for coloring printing inks, surface coatings and resins.///

This application is a continuation of application Ser. No. 776,222 filed Mar. 10, 1977 and now abandoned, which in turn was a continuation of application Ser. No. 561,004 filed Mar. 21, 1975 and now abandoned.

This application discloses and claims subject matter described in German Patent Application No. P 24 17 217.6, filed Apr. 9, 1974 and German Patent Application No. P 24 57 687.2, filed Dec. 6, 1974, which are incorporated herein by reference.

The present invention relates to dyes of the general formula I ##STR4## in which K is the radical of a coupling component, R³ and R⁴ independently of one another are hydrogen, chlorine, bromine, alkyl, alkoxy, nitro, cyano, alkylsulfonyl, arylsulfonyl, carboxyl, C-acylamino, carbamoyl, sulfamoyl, N-substituted carbamoyl or N-substituted sulfamoyl, carbalkoxy or quinazolonyl which may be substituted by chlorine, bromine or nitro, R² is hydrogen or ##STR5## CONHR¹ or SO₂ NHR, X is ##STR6## R is an optionally substituted aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radical and R¹ is hydrogen or a radical R, with the proviso that if ##STR7## Specific examples of R³ and R⁴, in addition to those mentioned above, are methyl, ethyl, methoxy, ethoxy, acetylamino, propionylamino, benzoylamino, propionylamino, benzoylamino, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, chlorophenylsulfonyl, N-phenyl-, N-chlorophenyl-, N-methylphenyl-, N-dichlorophenyl- or N-methoxyphenylcarbamoyl or N-methoxyphenylsulfamoyl, carbomethoxy and carboethoxy.

Preferably, R³ and R⁴ are hydrogen.

Examples of radicals R are alkyl of 1 to 8 carbon atoms, which may be substituted by hydroxyl, alkoxy of 1 to 4 carbon atoms, cyano, acyloxy, carbamoyl or N-substituted carbamoyl; cyclohexyl, benzyl, phenylethyl, styryl and phenyl; phenyl substituted by quinazolonyl, halogen, alkyl, alkoxy, alkylsulfonyl, cyano, nitro, carbamoyl, sulfamoyl, N-substituted carbamoyl or sulfamoyl, arylsulfonyl or acylamino; optionally N-substituted phthalimidyl, naphthyl, anthraquinonyl, pyridyl, 2,6-dihydroxypyridyl, quinazolonyl, quinolinyl, quinaldinyl and pyrimidinyl.

Specific examples of radicals R, in addition to those mentioned above, are: methyl, butyl, β-ethylhexyl, cyanomethyl, β-hydroxyethyl, β-ethoxyethyl, β-butoxyethyl, acetoxymethyl, carbamoylmethyl, N,N-dimethylcarbamoylmethyl, chlorophenyl, dichlorophenyl, methylphenyl, methoxyphenyl, methoxychlorophenyl, methoxydichlorophenyl, methylchlorophenyl, cyanophenyl, nitrophenyl, nitrochlorophenyl, nitromethoxyphenyl, nitromethylphenyl, sulfamoylphenyl, N-phenylsulfamoylphenyl, N-dichlorophenylsulfamoylphenyl, phenylsulfonylphenyl, acetylaminophenyl, benzoylaminophenyl, dichlorobenzoylaminophenyl and naphthoylaminophenyl as well as the radicals of the formulae ##STR8## wherein T is hydrogen, methyl, ethyl, propyl, butyl, phenyl, chlorophenyl, dichlorophenyl, methylchlorophenyl, methoxyphenyl, dimethylphenyl or dimethylchlorophenyl. Within the compass of the general definition, examples of R¹ are the same as those mentioned for R.

Examples of coupling components are compounds of the phenol, naphthol, acetoacetarylide, pyrazolone, quinoline, pyridone, pyrimidone and isoquinolone series.

Examples of individual coupling components are: phenol, o-, m- or p-cresol, α-naphthol, β-naphthol, 2-naphthol-3-carboxylic acid esters and amides, such as acetoacetanilide, acetoacet-o-anisidide, 1-phenyl-3-methyl-pyrazolone, 1-phenyl-pyrazolone-3-carboxylic acid esters or amides, 2,4-dihydroxyquinoline, N-methyl-4-hydroxy-quinolone-2, 2,6-dihydroxy-3-cyano-4-methylpyridine, 2,6-dihydroxy-3-carbamoyl-4-methylpyridine, N-methyl-, N-γ-methoxypropyl-, N-butyl- or N-benzyl-2-hydroxy-3-cyano-4-methyl-pyridone-6, 2-amino-4,6-dihydroxypyrimidine, 2,4-dihydroxy-6-aminopyrimidine, 2,4-diamino-6-hydroxy-pyrimidine, 1,3-dimethyl-4-hydroxy-pyrimidine-2,6-dione and 1,3-dihydroxyisoquinoline.

The dyes of the formula I may be prepared by reacting a diazo compound of amines of the formula II ##STR9## with a coupling component of the formula

    HK .

In the case of the manufacture of dyes with a 2-naphthol-3-carboxylic acid amide component, it can be advantageous to start from acid chlorides of the formula ##STR10## and convert these to the dye amides by reaction with the corresponding amines by conventional methods.

Dyes which may be used as pigments are in particular the compounds of the formula I wherein R is an aromatic radical and K is the radical of a coupling component of the β-naphthol, acetoacetarylide, pyrimidine, dihydroxyquinoline or dihydroxypyridine series. These dyes are highly insoluble in solvents and when used as pigments almost always exhibit good fastness to overcoating, to migration and to overspraying, and very good fastness to light. They can therefore be used, e.g., in printing inks, surface coatings or plastics such as PVC.

The pigments of the formula I are not always immediately obtained in the optimum physical form for particular end uses. However, they can be converted to the most suitable form by conventional methods such as grinding with salt, or heating in water or solvents.

The pigments of the invention may be used for pigmenting surface coatings and printing inks of all kinds, distempers and binder-based paints and for the mass coloring of synthetic, semisynthetic or natural macromolecular materials, e.g. polyvinyl chloride, polystyrene, polyamide or polyethylene. They may also be used for spin dyeing natural, regenerated or synthetic fibers, e.g. cellulose, polyester, polyacrylonitrile or nylon fibers. The pigments may be converted, by conventional methods, into pigment formulations, for example stable aqueous formulations for paints or for dyeing papers, or into nitrocellulose, PVC or other formulations which permit simple incorporation into the material to be colored.

The new dyes, especially those of the formula I a, have great tinctorial strength and brilliance and some of them have excellent fastness to light, very good fastness to overspraying, to solvents and to plasticizers, and good heat stability.

Other dyes of the formula I, in particular those wherein R is an aliphatic radical and the coupling component is a component of the cresol, N-alkylpyrimidine, N-alkylpyridine or N-alkylquinoline series, are good disperse dyes which may be used preferentially for dyeing polyester fibers and give dyeings of good fastness to light.

Dyes of the formula Ia ##STR11## wherein R⁵ is hydrogen, chlorine, bromine or nitro, R⁶ is hydrogen or ##STR12##

and K¹ is the radical of a coupling component of the acetoacetarylide or pyrimidone series and especially of the pyridone or 2-naphthol-3-carboxylic acid arylamide series and X has the above meaning, are of particularly great industrial importance.

In particular, the invention relates to dyes of the formula ##STR13## wherein K is ##STR14## Ar¹ is phenyl or phenyl substituted by chlorine, methoxy, ethoxy, methyl, acetylamino or benzoylamino, ##STR15## Ar² is phenyl or phenyl substituted by chlorine, methyl or sulfamoyl, Ar³ is phenyl, phenyl substituted by chlorine, bromine, nitro, methoxy, ethoxy, alkyl of 1 to 4 carbon atoms, carbamoyl, sulfamoyl, N-phenylcarbamoyl, N-chloro-, N-methyl- or N-methoxy-phenylcarbamoyl, N-β-anthraquinonyl-carbamoyl, phthalimido, benzoylamino, benzoylamino substituted by chlorine, methyl, methoxy or acetylamino, ##STR16## T¹ is methyl or carbamoyl, R² is cyano or carbamoyl,

T³ is hydroxyl or amino,

X is ##STR17## Z is ##STR18## hydrogen, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, nitro, cyano, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, chlorophenylsulfonyl, alkoxycarbonyl of 1 to 4 carbon atoms, CONHR¹ or SO₂ NHR,

R is phenyl; phenyl substituted by chlorine, bromine, hydroxyl, methoxy, ethoxy, alkyl of 1 to 4 carbon atoms, cyano, carbamoyl, nitro, phenyl, sulfamoyl, N-phenylsulfamoyl, acetylamino, benzoylamino or benzoylamino substituted by chlorine, methyl, hydroxyl, methoxy or ethoxy; naphthyl, N-phenylphthalimidyl, anthraquinonyl, pyridyl or styryl, and

R¹ is hydrogen; phenyl; phenyl substituted by chlorine, bromine, hydroxyl, methoxy, ethoxy, alkyl of 1 to 4 carbon atoms, cyano, carbamoyl, nitro, phenyl, sulfamoyl, N-phenylsulfamoyl, acetylamino, benzoylamino or benzoylamino substituted by chlorine, methyl, hydroxyl, methoxy or ethoxy; naphthyl, N-phenylphthalimidyl or anthraquinonyl, with the proviso that if ##STR19## Z is ##STR20## CONHR or SO₂ NHR¹.

Preferred radicals R are optionally substituted phenyl or naphthyl, wherein the substituents may be, e.g., chlorine, bromine, methyl, methoxy, ethoxy, cyano, nitro or optionally N-substituted carbamoyl or sulfamoyl.

Further valuable compounds are those with quinazolonyl and optionally N-substituted phthalimidyl radicals. Because of the available methods of synthesis, the compounds containing the radical ##STR21## are preferred. Pigments with two ##STR22## groups are also preferred.

In the preferred dyes, coupling components of the pyridone and pyrimidone series are free from substituents on the nitrogen atoms.

To manufacture the di-(1,3,4-oxdiazolyl)-anilines, the dichloride or dihydrazide of a dicarboxylic acid of the formula ##STR23## is reacted with carboxylic acid hydrazides or carboxylic acid chlorides of the formula ##STR24## and the diacyl hydrazides thus obtained are treated with a reducing agent and a dehydrating agent.

Details of the manufacture of the compounds may be found in the Examples wherein parts and percentages are by weight, unless stated otherwise.

Sulfamoyl-2-[1,3,4-oxdiazolyl]-anilines are obtained by reacting isatoic anhydrides of the formula ##STR25## with carboxylic acid hydrazides of the formula ##STR26## by conventional methods and then treating the products with dehydrating agents.

The sulfamoyl-substituted isatoic anhydrides may be obtained by reacting the corresponding ortho-halobenzoic acids (which are manufactured by, in part, conventional methods (U.P. Basu and S.J. De Gupta, J. Indian Chem. Soc. 16, 100 (1939)) first with ammonia and then with phosgene to give the corresponding isatoic anhydrides.

Corresponding carbamoyl-substituted 2-[1,3,4-oxdiazolyl]anilines are obtained analogously using correspondingly substituted anthranilic acids which have been manufactured analogously to the process of U.S. Pat. No. 2,808,433.

Synthesis of the other diazo components Process A

31 Parts of sodium carbonate in 200 parts of water together with 55 parts of benzonitrile in 250 parts of isobutanol and 45 parts of hydroxylammonium sulfate are boiled under reflux for 4 hours. The aqueous phase is then separated off and 85 parts of isatoic anhydride are introduced in portions into the isobutanol phase at from 90° to 100° C. The mixture is stirred for a further 10 minutes and 4 parts of finely powdered sodium methylate are added at the boil, whereupon 2-(3-phenyl-1,2,4-oxdiazolyl)-aniline separates out as a thick paste of crystals. After cooling, the product is filtered off, rinsed with a little isobutanol and dried. Yield 110 parts. Melting point: 128°-130° C.

Process B

25 parts of nitroterephthalic acid dichloride are added to 28 parts of benzamidoxime in 40 parts of N-methyl-pyrrolidone at 25° C. and the mixture is then stirred for 2 hours at 160° C. and cooled to 100° C. 10 parts of water are added and the resulting paste of crystals is filtered off at 10° C., washed with methanol and dried at 100° C. This gives 330 parts of 2,5-bis-(3-phenyl-1,2,4-oxdiazolyl)nitrobenzene which are suspended in 2,000 parts of alcohol; a solution of 540 parts of sodium dithionite in 2,000 parts of water is added in the course of 1 hour to this suspension at from 60° to 70° C. The pH is kept at 6 by simultaneously adding 2 N NaOH solution. The mixture is stirred for a further hour at from 70° to 80° C. and the product is filtered off, washed thoroughly with water and dried at 100° C. Yield: 277 parts of 2,5-bis-(3-phenyl-1,2,4-oxdiazolyl)aniline (melting point: 249°-250° C.)

Process C

43.3 Parts of 2-nitroterephthalic acid dinitrile, 36 parts of sodium carbonate in 150 parts of water, 51 parts of hydroxylammonium sulfate and 200 parts of isobutanol are boiled for 2 hours under reflux, during which time the 2-nitroterephthalic acid bis-amidoxime separates out as crystals. These are filtered off, washed with water and dried. Yield: 43 parts. Melting point: 199°-200° C.

48 Parts of this product are dissolved in 80 parts of N-methylpyrrolidone and 56.2 parts of benzoyl chloride are added at room temperatue. The temperature is then raised to 160° C. in the course of 2 hours after which the mixture is cooled, 100 ml of methanol are added and the product is filtered off and dried. Yield: 48 parts of 2,5-bis-(5-phenyl-1,2,4-oxdiazolyl)-nitrobenzene. Melting point: 203° C.

41 Parts of this product in 250 parts of glacial acetic acid are boiled under reflux and 26 parts of zinc dust are added in portions. After 3 hours the mixture is diluted with 200 parts of water and filtered, the residue is dissolved in hot dimethylformamide, this solution is filtered and the product is precipitated with water, again filtered off and dried at 100° C. This gives 31 parts of 2,5-bis-(5-phenyl-1,2,4-oxdiazolyl)-aniline. Melting point 213°-125° C.

Process D

18 Parts of 2-nitrobenzamidoxime are suspended in 50 parts of nitrobenzene, 15.5 parts of benzoyl chloride are added and the mixture is heated to 160° C. for 3 hours. It is then concentrated under reduced pressure and the product is filtered off and washed with a little cold alcohol. Yield: 21 parts of 2-(5-phenyl-1,2,4-oxdiazolyl)-nitrobenzene.

19 Parts of this product, in 100 parts of alcohol, are reduced with a solution of 50 parts of sodium dithionite in 180 parts of water in the course of 30 minutes at 65° C. The pH is kept at 6 by simultaneously adding sodium hydroxide solution. The mixture is stirred for a further 30 minutes at 70° C. and the product is filtered off, washed with water and dried. Yield: 11 parts of 2-(5-phenyl-1,2,4-oxdiazolyl)-aniline. Melting point: 123°-124° C.

Process E

44 Parts of 3,4-dihydro-4-oxoquinazoline-2-carboxylic acid ethyl ester, 39 parts of 2-amino-5-nitro-benzamidoxime and 3 parts of p-toluenesulfonic acid in 200 parts of nitrobenzene are slowly heated to 160° C. and kept at this temperature for 2 hours. When the mixture is cold, the product is filtered, rinsed with methanol and dried. This gives 50 parts of a compound of the formula ##STR27## which melts, with decomposition, from 354° C. onward.

EXAMPLE 1

59.3 Parts of 2-(3-phenyl-1,2,4-oxdiazlyl)-aniline are added at from 10° to 15° C. to 250 parts of 98% strength sulfuric acid and are diazotized, after cooling to 0° C., by adding 80 parts of 45% strength nitrosylsulfuric acid. The mixture is stirred for 3 hours at 5° C. and, after destroying the excess nitrite by adding urea, is poured onto a mixture of 1,200 parts of ice and 600 parts of water; a solution of 37.5 parts of 3-cyano-2,6-dihydroxy-4-methyl-pyridine in 1.2 l of 0.5 N NaOH is added and the pH is brought to 4-5 with dilute sodium hydroxide solution. The batch is stirred for a further 5 hours and the product is filtered off and washed thoroughly with warm water. On drying, 93 parts of a brilliant yellow powder of the formula ##STR28## are obtained.

Dyes of the stated hue are obtained analogously to Example 1 from the diazo components shown in the table which follows. The individual diazo components are synthesized analogously to Instruction A.

    __________________________________________________________________________     Ex.                                                                            No.                                                                               Diazo component         Coupling component              Hue                 __________________________________________________________________________         ##STR29##                                                                                              ##STR30##                      red                 3  "                                                                                                       ##STR31##                      reddish                                                                        orange              4  "                                                                                                       ##STR32##                      yellow              5  "                                                                                                       ##STR33##                      yellow              6  "                                                                                                       ##STR34##                      yellow              7  "                                                                                                       ##STR35##                      yellow              8  "                                                                                                       ##STR36##                      yellow              9  "                                                                                                       ##STR37##                      yellow              10 "                                                                                                       ##STR38##                      yellow              11 "                                                                                                       ##STR39##                      red                 12 "                                                                                                       ##STR40##                      red                 13 "                                                                                                       ##STR41##                      red                 14 "                                                                                                       ##STR42##                      red                 15                                                                                 ##STR43##                                                                                              ##STR44##                      yellow              16 "                                                                                                       ##STR45##                      yellow              17 "                                                                                                       ##STR46##                      yellow              18                                                                                 ##STR47##                                                                                              ##STR48##                      yellow              19 "                                                                                                       ##STR49##                      red                 20 "                                                                                                       ##STR50##                      yellow              21 "                                                                                                       ##STR51##                      yellow              22 "                                                                                                       ##STR52##                      yellow              23 "                                                                                                       ##STR53##                      yellow              24 "                                                                                                       ##STR54##                      yellow              25 "                                                                                                       ##STR55##                      yellow              26 "                                                                                                       ##STR56##                      yellow              27                                                                                 ##STR57##                                                                                              ##STR58##                      yellow              28 "                                                                                                       ##STR59##                      yellow              29 "                                                                                                       ##STR60##                      red                 30 "                                                                                                       ##STR61##                      red                 31 "                                                                                                       ##STR62##                      red                 32 "                                                                                                       ##STR63##                      red                 33 "                                                                                                       ##STR64##                      brownish red        34 "                                                                                                       ##STR65##                      red                 35 "                                                                                                       ##STR66##                      red                 36                                                                                 ##STR67##                                                                                              ##STR68##                      yellow              37 "                                                                                                       ##STR69##                      red                 38 "                                                                                                       ##STR70##                      red                 39 "                                                                                                       ##STR71##                      red                 40                                                                                 ##STR72##                                                                                              ##STR73##                      yellow              41 "                                                                                                       ##STR74##                      yellow              42 "                                                                                                       ##STR75##                      yellow              43 "                                                                                                       ##STR76##                      red                 44 "                                                                                                       ##STR77##                      red                 45                                                                                 ##STR78##                                                                                              ##STR79##                      yellow              46 "                                                                                                       ##STR80##                      yellow              47 "                                                                                                       ##STR81##                      yellow              48 "                                                                                                       ##STR82##                      red                 49 "                                                                                                       ##STR83##                      red                 50 "                                                                                                       ##STR84##                      red                 51 "                                                                                                       ##STR85##                      red                 52                                                                                 ##STR86##                                                                                              ##STR87##                      yellow              53 "                                                                                                       ##STR88##                      yellow              54 "                                                                                                       ##STR89##                      yellow              55 "                                                                                                       ##STR90##                      yellow              56 "                                                                                                       ##STR91##                      red                 57 "                                                                                                       ##STR92##                      red                 58 "                                                                                                       ##STR93##                      brownish red        59 "                                                                                                       ##STR94##                      red                 60 "                                                                                                       ##STR95##                      red                 61                                                                                 ##STR96##                                                                                              ##STR97##                      yellow              62 "                                                                                                       ##STR98##                      yellow              63 "                                                                                                       ##STR99##                      red                 64 "                                                                                                       ##STR100##                     red                 65                                                                                 ##STR101##                                                                                             ##STR102##                     yellow              66 "                                                                                                       ##STR103##                     yellow              67 "                                                                                                       ##STR104##                     red                 68 "                                                                                                       ##STR105##                     red                 69 "                                                                                                       ##STR106##                     red                 70                                                                                 ##STR107##                                                                                             ##STR108##                     yellow              71 "                                                                                                       ##STR109##                     red                 72                                                                                 ##STR110##                                                                                             ##STR111##                     yellow              73 "                                                                                                       ##STR112##                     yellow              74                                                                                 ##STR113##                                                                                             ##STR114##                     yellow              75 "                                                                                                       ##STR115##                     yellow              76 "                                                                                                       ##STR116##                     red                 77 "                                                                                                       ##STR117##                     red                 78 "                                                                                                       ##STR118##                     red                 79                                                                                 ##STR119##                                                                                             ##STR120##                     yellow              80 "                                                                                                       ##STR121##                     red                 81                                                                                 ##STR122##                                                                                             ##STR123##                     red                 82                                                                                 ##STR124##                                                                                             ##STR125##                     yellow              83 "                                                                                                       ##STR126##                     yellow              84 "                                                                                                       ##STR127##                     yellow              85 "                                                                                                       ##STR128##                     red                 86 "                                                                                                       ##STR129##                     red                 87                                                                                 ##STR130##                                                                                             ##STR131##                     yellow              88 "                                                                                                       ##STR132##                     red                 89                                                                                 ##STR133##                                                                                             ##STR134##                     yellow              90 "                                                                                                       ##STR135##                     red                 91                                                                                 ##STR136##                                                                                             ##STR137##                     yellow              92 "                                                                                                       ##STR138##                     yellow              93 "                                                                                                       ##STR139##                     red                 94 "                                                                                                       ##STR140##                     red                 95                                                                                 ##STR141##                                                                                             ##STR142##                     yellow              96 "                                                                                                       ##STR143##                     red                 97                                                                                 ##STR144##                                                                                             ##STR145##                     yellow              98 "                                                                                                       ##STR146##                     yellow              99 "                                                                                                       ##STR147##                     yellow              100                                                                               "                                                                                                       ##STR148##                     yellow              101                                                                               "                                                                                                       ##STR149##                     red                 102                                                                               "                                                                                                       ##STR150##                     red                 103                                                                               "                                                                                                       ##STR151##                     red                 104                                                                                ##STR152##                                                                                             ##STR153##                     yellow              105                                                                               "                                                                                                       ##STR154##                     yellow              106                                                                                ##STR155##                                                                                             ##STR156##                     red                 107                                                                               "                                                                                                       ##STR157##                     red                 108                                                                                ##STR158##                                                                                             ##STR159##                     yellow              109                                                                               "                                                                                                       ##STR160##                     yellow              110                                                                               "                                                                                                       ##STR161##                     red                 111                                                                               "                                                                                                       ##STR162##                     red                 112                                                                               "                                                                                                       ##STR163##                     red                 113                                                                                ##STR164##                                                                                             ##STR165##                     yellow              114                                                                               "                                                                                                       ##STR166##                     yellow              115                                                                               "                                                                                                       ##STR167##                     red                 116                                                                                ##STR168##                                                                                             ##STR169##                     red                 117                                                                               "                                                                                                       ##STR170##                     red                 118                                                                               "                                                                                                       ##STR171##                     red                 119                                                                                ##STR172##                                                                                             ##STR173##                     yellow              120                                                                               "                                                                                                       ##STR174##                     yellow              121                                                                               "                                                                                                       ##STR175##                     red                 122                                                                                ##STR176##                                                                                             ##STR177##                     yellow              123                                                                               "                                                                                                       ##STR178##                     red                 124                                                                               "                                                                                                       ##STR179##                     red                 125                                                                                ##STR180##                                                                                             ##STR181##                     yellow              126                                                                               "                                                                                                       ##STR182##                     red                 127                                                                               "                                                                                                       ##STR183##                     red                 128                                                                               "                                                                                                       ##STR184##                     red                 129                                                                                ##STR185##                                                                                             ##STR186##                     yellow              130                                                                               "                                                                                                       ##STR187##                     red                 131                                                                               "                                                                                                       ##STR188##                     red                 132                                                                                ##STR189##                                                                                             ##STR190##                     yellow              133                                                                               "                                                                                                       ##STR191##                     yellow              134                                                                               "                                                                                                       ##STR192##                     red                                                                             redTR193##         136                                                                               "                                                                                                       ##STR194##                                         137                                                                               "                                                                                                       ##STR195##                     red                 138                                                                                ##STR196##                                                                                             ##STR197##                     yellow              139                                                                               "                                                                                                       ##STR198##                     red -140                                                                        redTR199##         141                                                                               "                                                                                                       ##STR200##                     red                 142                                                                                ##STR201##                                                                                             ##STR202##                     yellow              143                                                                                ##STR203##                                                                                             ##STR204##                     yellow              144                                                                               "                                                                                                       ##STR205##                     red                 145                                                                                ##STR206##                                                                                             ##STR207##                     yellow              146                                                                               "                                                                                                       ##STR208##                     red -147                                                                        redTR209##         148                                                                                ##STR210##                                                                                             ##STR211##                     yellow              149                                                                               "                                                                                                       ##STR212##                     red                 150                                                                               "                                                                                                       ##STR213##                     red                 151                                                                               "                                                                                                       ##STR214##                     red                 152                                                                                ##STR215##                                                                                             ##STR216##                     yellow              153                                                                               "                                                                                                       ##STR217##                     yellow              154                                                                               "                                                                                                       ##STR218##                     red                 155                                                                               "                                                                                                       ##STR219##                     red                 156                                                                                ##STR220##                                                                                             ##STR221##                     yellow              157                                                                               "                                                                                                       ##STR222##                     red                 158                                                                               "                                                                                                       ##STR223##                     red                 159                                                                                ##STR224##                                                                                             ##STR225##                     yellow              160                                                                               "                                                                                                       ##STR226##                     red                 161                                                                                ##STR227##                                                                                             ##STR228##                     red                 __________________________________________________________________________

EXAMPLE 162

19.1 Parts of 2,5-bis-(3-phenyl-1,2,4-oxdiazolyl)-aniline are introduced into a mixture of 100 parts of glacial acetic acid and 100 parts of propionic acid and diazotized at 0°-5° C. by adding 15 parts of 45% strength nitrosylsulfuric acid. The mixture is stirred for a further 4 hours at 5° C. and a solution of 13.2 parts of 2-naphthol-3-carboxylic acid N-phenylamide in 150 parts of dimethylformamide is then added, followed by 70 parts of pyridine added slowly. The mixture is stirred for a further 6 hours at room temperature and then for 2 hours at 80° C. and the product is filtered off, washed thoroughly with water and methanol and dried at 80° C. This gives 25 parts of a reddish orange powder of the formula ##STR229##

EXAMPLES 163-251

The procedure described in Example 162 is followed, using the diazo components and coupling components shown in the table. The individual diazo components are manufactured according to Instructions A to E, as shown alongside the diazo component in the table.

    __________________________________________________________________________     Ex.                                                                            No.                                                                               Diazo component               Coupling component       Hue                  __________________________________________________________________________     163                                                                                ##STR230##                                                                                                   ##STR231##              yellow               164                                                                               "                                                                                                             ##STR232##              reddish orange       165                                                                                ##STR233##                                                                                                   ##STR234##              reddish orange       166                                                                                ##STR235##                                                                                                   ##STR236##              yellow               167                                                                               "                                                                                                             ##STR237##              reddish orange       168                                                                                ##STR238##                                                                                                   ##STR239##              red                  169                                                                               "                                                                                                             ##STR240##              red                  170                                                                                ##STR241##                                                                                                   ##STR242##              yellow               171                                                                               "                                                                                                             ##STR243##              red                  172                                                                               "                                                                                                             ##STR244##              red                  173                                                                                ##STR245##                                                                                                   ##STR246##              yellow               174                                                                               "                                                                                                             ##STR247##              red                  175                                                                                ##STR248##                                                                                                   ##STR249##              yellow               176                                                                               "                                                                                                             ##STR250##              red                  177                                                                               "                                                                                                             ##STR251##              red                  178                                                                                ##STR252##                                                                                                   ##STR253##              yellow               179                                                                               "                                                                                                             ##STR254##              yellow               180                                                                               "                                                                                                             ##STR255##              red                  181                                                                               "                                                                                                             ##STR256##              red                  182                                                                                ##STR257##                                                                                                   ##STR258##              yellow               183                                                                               "                                                                                                             ##STR259##              red                  184                                                                               "                                                                                                             ##STR260##              red                  185                                                                                ##STR261##                                                                                                   ##STR262##              red                  186                                                                                ##STR263##                                                                                                   ##STR264##              yellow               187                                                                               "                                                                                                             ##STR265##              red                  188                                                                               "                                                                                                             ##STR266##              red                  189                                                                                ##STR267##                                                                                                   ##STR268##              red                  190                                                                               "                                                                                                             ##STR269##              red                  191                                                                                ##STR270##                                                                                                   ##STR271##              red                  192                                                                                ##STR272##                                                                                                   ##STR273##              yellow               193                                                                               "                                                                                                             ##STR274##              yellow               194                                                                               "                                                                                                             ##STR275##              red                  195                                                                               "                                                                                                             ##STR276##              red                  196                                                                                ##STR277##                                                                                                   ##STR278##              yellow               197                                                                               "                                                                                                             ##STR279##              red                  198                                                                                ##STR280##                                                                                                   ##STR281##              red                  199                                                                               "                                                                                                             ##STR282##              yellow               200                                                                                ##STR283##                                                                                                   ##STR284##              yellow               201                                                                               "                                                                                                             ##STR285##              red                  202                                                                                ##STR286##                                                                                                   ##STR287##              red                  203                                                                               "                                                                                                             ##STR288##              red                  204                                                                                ##STR289##                                                                                                   ##STR290##              red                  205                                                                               "                                                                                                             ##STR291##              red                  206                                                                                ##STR292##                                                                                                   ##STR293##              yellow               207                                                                               "                                                                                                             ##STR294##              yellow               208                                                                                ##STR295##                                                                                                   ##STR296##              red                  209                                                                               "                                                                                                             ##STR297##              red                  210                                                                               "                                                                                                             ##STR298##              red                  211                                                                                ##STR299##                                                                                                   ##STR300##              yellow               212                                                                               "                                                                                                             ##STR301##              red                  213                                                                                ##STR302##                                                                                                   ##STR303##              yellow               214                                                                               "                                                                                                             ##STR304##              red                  215                                                                                ##STR305##                                                                                                   ##STR306##              red                  216                                                                               "                                                                                                             ##STR307##              red                  217                                                                                ##STR308##                                                                                                   ##STR309##              yellow               218                                                                               "                                                                                                             ##STR310##              yellow               219                                                                               "                                                                                                             ##STR311##              red                  220                                                                                ##STR312##                                                                                                   ##STR313##              red                  221                                                                                ##STR314##                                                                                                   ##STR315##              yellow               222                                                                               "                                                                                                             ##STR316##              red                  223                                                                                ##STR317##                                                                                                   ##STR318##              yellow               224                                                                               "                                                                                                             ##STR319##              yellow               225                                                                               "                                                                                                             ##STR320##              red                  226                                                                                ##STR321##                                                                                                   ##STR322##              red                  227                                                                               "                                                                                                             ##STR323##              red                  228                                                                                ##STR324##                                                                                                   ##STR325##              red                  229                                                                               "                                                                                                             ##STR326##              red                  230                                                                                ##STR327##                                                                                                   ##STR328##              yellow               231                                                                               "                                                                                                             ##STR329##              red                  232                                                                                ##STR330##                                                                                                   ##STR331##              red                  233                                                                                ##STR332##                                                                                                   ##STR333##              yellow               234                                                                               "                                                                                                             ##STR334##              yellow               235                                                                               "                                                                                                             ##STR335##              red                  236                                                                                ##STR336##                                                                                                   ##STR337##              yellow               237                                                                                ##STR338##                                                                                                   ##STR339##              yellow               238                                                                               "                                                                                                             ##STR340##              red                  239                                                                               "                                                                                                             ##STR341##              red                  240                                                                                ##STR342##                                                                                                   ##STR343##              yellow               241                                                                               "                                                                                                             ##STR344##              red                  242                                                                                ##STR345##                                                                                                   ##STR346##              yellow               243                                                                               "                                                                                                             ##STR347##              red                  244                                                                                ##STR348##                                                                                                   ##STR349##              red                  245                                                                                ##STR350##                                                                                                   ##STR351##              yellow               246                                                                                ##STR352##                                                                                                   ##STR353##              yellow               247                                                                                ##STR354##                                                                                                   ##STR355##              red                  248                                                                               "                                                                                                             ##STR356##              yellow               249                                                                                ##STR357##                                                                                                   ##STR358##              red                  250                                                                                ##STR359##                                                                                                   ##STR360##              yellow               251                                                                               "                                                                                                             ##STR361##              red                  __________________________________________________________________________

EXAMPLE 252

The procedure followed is as in Example 1, except that 47 parts of β-hydroxynaphthoic acid are used as the coupling component. After completion of coupling, the mixture is acidified to pH 1 with dilute sulfuric acid and the product is filtered off, washed thoroughly with water and dried. This gives 106 parts of the acid ##STR362##

437 Parts of this acid in 1,800 parts of dichlorobenzene, 2 parts of dimethylformamide and 350 parts of thionyl chloride are heated for one hour at 100° C., 2 hours at 115° C. and 1 hour at 125° C. and then cooled; the product is filtered off, washed with toluene and dried. This gives 336 parts of the acid chloride.

22.3 parts of this acid chloride are introduced into 200 parts of nitrobenzene, 22 parts of p-aminobenzanilide are added and the mixture is stirred for 1 hour at 90° C., 1 hour at 110° C. and 2 hours at 130° C. The product is then filtered off at 60° C., washed with nitrobenzene and methanol and dried. This gives 36 parts of a red powder of the formula ##STR363##

EXAMPLES 253-300

The dyes shown in the table which follows, and having the stated hue, are obtained analogously to Example 252 from the carboxylic acid chlorides, and amines also shown in the table.

    __________________________________________________________________________     Example                                                                        No.  Carboxylic acid chloride                                                                          Amine                             Hue                  __________________________________________________________________________     253                                                                                  ##STR364##                                                                                        ##STR365##                       red                  254  "                                                                                                  ##STR366##                       red                  255  "                                                                                                  ##STR367##                       red                  256  "                                                                                                  ##STR368##                       red                  257  "                                                                                                  ##STR369##                       red                  258  "                                                                                                  ##STR370##                       red                  259  "                                                                                                  ##STR371##                       red                  260  "                                                                                                  ##STR372##                       red                  261  "                                                                                                  ##STR373##                       red                  262  "                                                                                                  ##STR374##                       red                  263  "                                                                                                  ##STR375##                       red                  264  "                                                                                                  ##STR376##                       red                  265  "                                                                                                  ##STR377##                       red                  266  "                                                                                                  ##STR378##                       red                  267                                                                                  ##STR379##                                                                                        ##STR380##                       red                  268  "                                                                                                  ##STR381##                       red                  269  "                                                                                                  ##STR382##                       red                  270  "                                                                                                  ##STR383##                       red                  271  "                                                                                                  ##STR384##                       red                  272  "                                                                                                  ##STR385##                       red                  273  "                                                                                                  ##STR386##                       red                  274  "                                                                                                  ##STR387##                       red                  275  "                                                                                                  ##STR388##                       red                  276  "                                                                                                  ##STR389##                       red                  277  "                                                                                                  ##STR390##                       red                  278  "                                                                                                  ##STR391##                       red                  279  "                                                                                                  ##STR392##                       red                  280  "                                                                                                  ##STR393##                       red                  281  "                                                                                                  ##STR394##                       red                  282  "                                                                                                  ##STR395##                       red                  283                                                                                  ##STR396##                                                                                        ##STR397##                       maroon               284  "                                                                                                  ##STR398##                       red                  285  "                                                                                                  ##STR399##                       red                  286  "                                                                                                  ##STR400##                       maroon               287  "                                                                                                  ##STR401##                                            288                                                                                  ##STR402##                                                                                        ##STR403##                       red                  289  "                                                                                                  ##STR404##                       red                  290  "                                                                                                  ##STR405##                       red                  291  "                                                                                                  ##STR406##                       red                  292  "                                                                                                  ##STR407##                       red                  293  "                                                                                                  ##STR408##                       red                  294                                                                                  ##STR409##                                                                                        ##STR410##                       reddish orange       295  "                                                                                                  ##STR411##                       reddish orange       296  "                                                                                                  ##STR412##                       red                  297  "                                                                                                  ##STR413##                       red                  298  "                                                                                                  ##STR414##                       reddish orange       299  "                                                                                                  ##STR415##                       red                  300  "                                                                                                  ##STR416##                       red                  __________________________________________________________________________

EXAMPLE 301

84 Parts of benzoyl chloride are added dropwise to a suspension of 60 parts of nitroterephthalic acid dihydrazide in 250 parts to toluene at room temperature, and after one hour a solution of 53 parts of sodium hydroxide in 450 parts of water is added. The mixture is stirred for a further hour and is then acidified and the product is filtered off, washed with alcohol and with water and dried. 88.6 parts of nitroterephthalic acid N',N'-dibenzoyl-dihydrazide of melting point 295°-298° are obtained.

624 Parts of nitroterephthalic acid N',N'-dibenzoyl-dihydrazide are dissolved in 4,000 parts of dimethylformamide at 80° C. and hydrogenated in the presence of Raney nickel. The mixture is filtered hot and the product is precipitated with water, filtered off, washed with water and dried. 530 Parts of aminoterephthalic acid N',N'-dibenzoyl-dihydrazide of melting point 305° are obtained.

530 Parts of aminoterephthalic acid N',N'-dibenzoyl-dihydrazide in 2,000 parts of POCl₃ are heated under reflux until a clear solution has been produced. After cooling, the product is precipitated by pouring the mixture onto ice and is filtered off, washed with water and dried. 490 parts of 2,5-bis-[5-phenyl-1,3,4-oxidiazolyl]-aniline of melting point 294° are obtained.

38.1 Parts of 2,5-bis-[5-phenyl-1,3,4-oxdiazolyl]-aniline are introduced into 200 parts of a 1:1 mixture of glacial acetic acid and propionic acid, cooled to from 0 to 5° C. and diazotized, at this temperature, by adding 30 parts by volume of nitrosylsulfuric acid. The mixture is stirred for 4 hours at 5° C., 50 parts of urea are then added, and a solution of 29.7 parts of β-hydroxynaphthoic acid p-chloroanilide in 300 parts of dimethylformamide and 98 parts of triethanolamine is added dropwise at a rate such that the temperature does not rise above 15° C. The mixture is then stirred for 10 hours at room temperature and 1 hour at 70° C. and the product is filtered off hot and washed thoroughly with dimethylformamide and with water. The paste obtained is added to 400 parts of methanol, the mixture is heated under reflux for one hour and the product is filtered off hot, washed with methanol and dried.

46 Parts of a bluish red powder of the formula ##STR417## are obtained.

EXAMPLES 302-321

Analogously to Example 301, the coupling components shown in the table which follows give the corresponding dyes, having the hue shown in the table.

    __________________________________________________________________________     Example No.                                                                           Coupling component             Hue                                      __________________________________________________________________________     302                                                                                    ##STR418##                    bluish red                               303                                                                                    ##STR419##                    red                                      304                                                                                    ##STR420##                    red                                      305                                                                                    ##STR421##                    red                                      306                                                                                    ##STR422##                    reddish orange                           307                                                                                    ##STR423##                    red                                      308                                                                                    ##STR424##                    bluish red                               309                                                                                    ##STR425##                    reddish brown                            310                                                                                    ##STR426##                    reddish brown                            311                                                                                    ##STR427##                    reddish brown                            312                                                                                    ##STR428##                    red                                      313                                                                                    ##STR429##                    red                                      314                                                                                    ##STR430##                    red                                      315                                                                                    ##STR431##                    yellow                                   316                                                                                    ##STR432##                    yellow                                   317                                                                                    ##STR433##                    yellow                                   318                                                                                    ##STR434##                    yellow                                   319                                                                                    ##STR435##                    yellow                                   320                                                                                    ##STR436##                    yellow                                   321                                                                                    ##STR437##                    yellow                                   __________________________________________________________________________

EXAMPLE 322

22.5 Parts of 2,5-bis-[5-(p-chlorophenyl)-1,3,4-oxidiazolyl]-aniline are introduced into 200 parts of a 1:1 mixture of glacial acetic acid and propionic acid, cooled to from 0° to 5° C. and diazotized, at this temperature, by adding 15 parts of volume of nitrosylsulfuric acid. The mixture is stirred for one hour, 270 parts of sulfuric acid are added to produce complete solution, and the mixture is then stirred for a further 4 hours. Thereafter the product is precipitated by pouring the mixture onto ice, 25 parts of urea are added to the batch and the product is filtered off. The filter cake is worked into a paste with dimethylformamide and this paste is added to a solution of 14.87 parts of β-hydroxynaphthoic acid p-chloroanilide in 500 parts of dimethylformamide. The pH is brought to from 5 to 6 by adding pyridine. The mixture is stirred overnight and the product is then filtered off and washed with dimethylformamide, water and methanol. After drying, 33.6 parts of a red powder of the formula ##STR438## are obtained.

The coupling components listed in the table which follows analogously give the corresponding dyes;

    ______________________________________                                         Example No.                                                                             Coupling component      Hue                                           ______________________________________                                         323                                                                                      ##STR439##             red                                           324                                                                                      ##STR440##             red                                           325                                                                                      ##STR441##             red                                           326                                                                                      ##STR442##             red                                           327                                                                                      ##STR443##             reddish orange                                328                                                                                      ##STR444##             red                                           329                                                                                      ##STR445##             red                                           330                                                                                      ##STR446##             red                                           331                                                                                      ##STR447##             reddish orange                                332                                                                                      ##STR448##             red                                           333                                                                                      ##STR449##             red                                           334                                                                                      ##STR450##             red                                           335                                                                                      ##STR451##             red                                           336                                                                                      ##STR452##             red                                           337                                                                                      ##STR453##             yellow                                        338                                                                                      ##STR454##             yellow                                        339                                                                                      ##STR455##             yellow                                        340                                                                                      ##STR456##             yellow                                        341                                                                                      ##STR457##             yellow                                        ______________________________________                                    

EXAMPLE 342-349

The procedure followed is as in Example 22, except that the diazo component is 3,5-bis-[5-phenyl-1,3,4-oxdiazoyl]-aniline and the coupling components shown in the table are used. The corresponding dyes, having the hue shown in the table, as obtained:

    ______________________________________                                         Example No.                                                                             Coupling component     Hue                                            ______________________________________                                         342                                                                                      ##STR458##            reddish orange                                 343                                                                                      ##STR459##            reddish orange                                 344                                                                                      ##STR460##            reddish orange                                 345                                                                                      ##STR461##            yellow                                         346                                                                                      ##STR462##            yellow                                         347                                                                                      ##STR463##            grey- ish yellow                               348                                                                                      ##STR464##            yellow                                         349                                                                                      ##STR465##            yellow                                         ______________________________________                                    

EXAMPLE 350-367

The procedure followed is as in Example 322, except that the diazo component is 2,5-bis-[5(p-methoxyphenyl)-1,3,4-oxdiazoyl]-aniline and the coupling components shown in the table are used. The corresponding dyes, having the hue shown in the table, are obtained:

    ______________________________________                                         Example No.                                                                             Coupling component     Hue                                            ______________________________________                                         350                                                                                      ##STR466##            reddish brown                                  351                                                                                      ##STR467##            reddish brown                                  352                                                                                      ##STR468##            red                                            353                                                                                      ##STR469##            bluish red                                     354                                                                                      ##STR470##            red                                            355                                                                                      ##STR471##            red                                            356                                                                                      ##STR472##            red                                            357                                                                                      ##STR473##            red                                            358                                                                                      ##STR474##            red                                            359                                                                                      ##STR475##            red                                            360                                                                                      ##STR476##            red                                            361                                                                                      ##STR477##            red                                            362                                                                                      ##STR478##            red                                            363                                                                                      ##STR479##            yellow                                         364                                                                                      ##STR480##            yellow                                         365                                                                                      ##STR481##            yellow                                         366                                                                                      ##STR482##            greenish yellow                                ______________________________________                                    

EXAMPLES 367-383

The procedure followed is as in Example 322, except that the diazo component is 2,5-bis-[5(2,4-dichlorophenyl)-1,3,4-oxdiazolyl]-aniline and the coupling components shown in the table are used. The corresponding dyes, having the hue shown in the table, are obtained:

    ______________________________________                                         Example No.                                                                             Coupling component     Hue                                            ______________________________________                                         367                                                                                      ##STR483##            red                                            368                                                                                      ##STR484##            reddish brown                                  369                                                                                      ##STR485##            brown                                          370                                                                                      ##STR486##            red                                            371                                                                                      ##STR487##            red                                            372                                                                                      ##STR488##            reddish brown                                  373                                                                                      ##STR489##            reddish brown                                  374                                                                                      ##STR490##            red                                            375                                                                                      ##STR491##            red                                            376                                                                                      ##STR492##            red                                            377                                                                                      ##STR493##            red                                            378                                                                                      ##STR494##            reddish brown                                  379                                                                                      ##STR495##            reddish brown                                  380                                                                                      ##STR496##            yellow                                         381                                                                                      ##STR497##            yellow                                         382                                                                                      ##STR498##            yellow                                         383                                                                                      ##STR499##            yellow                                         ______________________________________                                    

EXAMPLE 384-386

The procedure followed is as in Example 301, except that the diazo component is 2,5-bis-[-5-(α-naphthyl)-1,3,4-oxdizolyl]-aniline and the coupling components shown in the table are used. The corresponding dyes, having the hue shown in the table, are obtained:

    ______________________________________                                         Example No.                                                                             Coupling component      Hue                                           ______________________________________                                         384                                                                                      ##STR500##             red                                           385                                                                                      ##STR501##             red                                           386                                                                                      ##STR502##             red                                           ______________________________________                                    

EXAMPLES 387-392

The procedure followed is as in Example 301, except that the diazo component is 3,5-bis[-5-(β-naphthyl)-1,3,4-oxdiazolyl]-aniline and the coupling components shown in the table are used. The corresponding dyes, having the hue shown in the table, are obtained:

    ______________________________________                                         Ex.                                                                            No.  Coupling component           Hue                                          ______________________________________                                         387                                                                                  ##STR503##                  red                                          388                                                                                  ##STR504##                  red                                          389                                                                                  ##STR505##                  red                                          390                                                                                  ##STR506##                  red                                          391                                                                                  ##STR507##                  red                                          392                                                                                  ##STR508##                  red                                          ______________________________________                                    

EXAMPLE 393-394

4-Chloro-2,5-bis-5-phenyl-1,3,4-oxdiazolyl-aniline is prepared analogously to Example 301 from 3-chloro-6-nitroterephthalic acid dihydrazide and is diazotized, and coupled, as described in Example 301. Using the coupling components shown in the table, the corresponding dyes, having the hue shown in the table, are obtained:

    ______________________________________                                         Ex.                                                                            No.  Coupling component           Hue                                          ______________________________________                                         393                                                                                  ##STR509##                  red                                          394                                                                                  ##STR510##                  red                                          ______________________________________                                    

EXAMPLES 395-401

3,5-bis-[5-p-chlorophenyl-1,3,4-oxdiazolyl]-aniline is prepared analogously to Example 301 and is diazotized, and coupled, as indicated in Example 322. Using the coupling components shown in the table which follows, the corresponding dyes, having the hue shown in the table, are obtained:

    ______________________________________                                         Example No.                                                                             Coupling component      Hue                                           ______________________________________                                         395                                                                                      ##STR511##             red                                           396                                                                                      ##STR512##             red                                           397                                                                                      ##STR513##             red                                           398                                                                                      ##STR514##             yellow                                        399                                                                                      ##STR515##             yellow                                        340                                                                                      ##STR516##             yellow                                        401                                                                                      ##STR517##             yellow                                        ______________________________________                                    

EXAMPLE 402

94.8 Parts of 2,5-bis-[5-phenyl-1,3,4-oxdiazolyl]-aniline are introduced into 500 parts of concentrated sulfuric acid at from 10° to 15° C. and after cooling from 0° to 5° C. are diazotized by adding 75 ccs of nitrosylsulfuric acid. The mixture is stirred for 5 hours and then poured onto 4 kg of ice, and urea is added. 46.1 parts of finely powdered β-hydroxynaphthoic acid are then added, followed by dilute sodium hydroxide solution until the pH is from 6 to 7. After completion of coupling, the mixture is acidified to pH 1 with dilute sulfuric acid and the product is filtered off, washed thoroughly with water and dried. This gives 137 parts of the acid of the formula ##STR518##

137 Parts of this acid in 1,400 parts of thionyl chloride are heated under reflux for 7 hours. The thionyl chloride is then distilled off and the residue is taken up in petroleum ether, filtered off, washed with petroleum ether and dried. This gives 134 parts of the acid chloride of the formula ##STR519##

11.9 Parts of this acid chloride are introduced into 150 parts by volume of dry nitrobenzene, 3.24 parts of 3,4-dichloroaniline are added and the mixture is stirred for 1 hour at 110° C. and 4 hours at 130° C. The product is then filtered off, washed with nitrobenzene, dimethylformamide and methanol and dried, giving 3.6 parts of the dye of the formula ##STR520##

EXAMPLE 403-418

The procedure followed is as in Example 402 except that the amines shown in the table are used in place of 3,4-dichloroaniline. The corresponding dyes, having the hue shown in the table, are obtained:

    ______________________________________                                         Example No.                                                                             Amine               Hue                                               ______________________________________                                         403                                                                                      ##STR521##         reddish orange                                    404                                                                                      ##STR522##         red                                               405                                                                                      ##STR523##         reddish orange                                    406                                                                                      ##STR524##         red                                               407                                                                                      ##STR525##         bluish red                                        408                                                                                      ##STR526##         red                                               409                                                                                      ##STR527##         red                                               410                                                                                      ##STR528##         red                                               411                                                                                      ##STR529##         bluish red                                        412                                                                                      ##STR530##         reddish orange                                    413                                                                                      ##STR531##         bluish red                                        414                                                                                      ##STR532##         red                                               415                                                                                      ##STR533##         reddish orange                                    416                                                                                      ##STR534##         red                                               417                                                                                      ##STR535##         red                                               418                                                                                      ##STR536##         bluish red                                        ______________________________________                                    

EXAMPLE 419

800 parts of o-chlorobenzoic acid in 2,400 parts of chlorosulfonic acid are stirred for 10 hours at from 85° to 90° C. The product is then precipitated by pouring the mixture onto ice and is filtered off, washed thoroughly with water and dried. This gives 970 parts of a colorless powder of the formula ##STR537##

602 Parts of 2-chloro-5-chlorosulfonylbenzoic acid are added to a solution of 830 parts of 2,4-dichloroaniline in 600 parts of toluene at 60° and the mixture is stirred for 6 hours at the same temperature. Insoluble material is then dissolved in dilute sodium hydroxide solution, the aqueous layer is separated off and acidified with dilute hydrochloric acid and the product is filtered off and washed with water. After redissolving in sodium hydroxide solution, reprecipitation with hydrochloric acid and drying, 592 parts of 2-chloro-5-[2,4-dichlorophenyl-sulfamoyl]-benzoic acid are obtained as a colorless powder of melting point 174° C.

Cl: calculated 28.1%, found 28.4%.

280 Parts of this compound, in 1,500 parts of 20 percent strength ammonia, are stirred with 2 parts of copper-(I) chloride for 8 hours at 150° C. After the mixture has cooled, it is acidified and the product is filtered off, washed with water and dried. This gives 246 parts of 5-[2,4-dichlorophenyl-sulfamoyl]-anthranilic acid of melting point 224° C.

Cl: calculated 19.6%, found 19.6%.

179 parts of the above anthranilic acid are suspended in 800 parts of dioxane and phosgene is passed into this suspension for 8 hours at room temperature. The suspension is then purged with nitrogen and the product is filtered off, washed with ice water and dried. This gives 123 parts of 5-[2,4-dichlorophenyl-sulfamoyl] isatoic anhydride of melting point 215° C.

97 Parts of this isatoic anhydride are dissolved in 200 parts of N-methylpyrrolidone and 35 parts of benzhydrazide are added. The mixture is stirred at 120° C. until the evolution of CO₂ is ceased, 35 parts of phosphorus pentoxide are then added and the batch is stirred for a further 4 hours at 120° C. After cooling, the product is precipitated with water, filtered off, rinsed with water and dried. This gives 107 parts of 4-[2,4-dichlorophenyl-sulfamoyl]-2 [5-phenyl-1,3,4-oxdiazolyl]-aniline of meltingpoint 215°-220° C.

23 parts of 4-[2,4-dichlorophenyl-sulfamoyl]-2-[5-phenyl-1,3,4-oxdiazolyl]-aniline are added to 300 parts of a 1:1 mixture glacial acetic acid and propionic acid, and are diazotized with 25 parts by volume of nitrosylsulfuric acid at from 0° to 5° C. The mixture is stirred for 4 hours at 5° C., 50 parts of urea are added and a solution of 13.65 parts of β-hydroxynaphthoic acid anilide in 200 parts of methanol and 20 parts of 50% strength sodium hydroxide solution is run in slowly. The pH is brought to from 5 to 6 with dilute sodium hydroxide solution and the mixture is stirred overnight. The product is then filtered off and washed with methanol and with water. The moist paste is stirred with methylglycol at from 90° to 100° C.for one hour and the product is then filtered off hot, washed with methylglycol and water and dried. This gives 28.4 parts of a red powder of the formula ##STR538##

EXAMPLE 420-451

The procedure followed is as in Example 419 but in place of 2,4-dichloroaniline the amines indicated in the table are employed; using the coupling components also shown, the corresponding dyes, having the hue shown in the table, are obtained:

    __________________________________________________________________________     Example No.                                                                           Amine               Coupling component         Hue                      __________________________________________________________________________     420                                                                                    ##STR539##                                                                                         ##STR540##                reddish orange           421    "                                                                                                   ##STR541##                red                      422    "                                                                                                   ##STR542##                reddish brown            423    "                                                                                                   ##STR543##                greenish yellow          424    "                                                                                                   ##STR544##                greenish yellow          425    "                                                                                                   ##STR545##                greenish yellow          426    "                                                                                                   ##STR546##                greenish yellow          427                                                                                    ##STR547##                                                                                         ##STR548##                reddish orange           428    "                                                                                                   ##STR549##                reddish orange           429    "                                                                                                   ##STR550##                reddish brown            430    "                                                                                                   ##STR551##                reddish brown            431    "                                                                                                   ##STR552##                reddish brown            432    "                                                                                                   ##STR553##                red                      433    "                                                                                                   ##STR554##                yellow                   434    "                                                                                                   ##STR555##                yellow                   435    "                                                                                                   ##STR556##                yellow                   436                                                                                    ##STR557##                                                                                         ##STR558##                reddish orange           437    "                                                                                                   ##STR559##                red                      438    "                                                                                                   ##STR560##                red                      439    "                                                                                                   ##STR561##                bluish red               440    "                                                                                                   ##STR562##                red                      441    "                                                                                                   ##STR563##                bluish red               442    "                                                                                                   ##STR564##                orange                   443    "                                                                                                   ##STR565##                orange                   444    "                                                                                                   ##STR566##                yellow                   445    "                                                                                                   ##STR567##                yellow                   446    "                                                                                                   ##STR568##                yellow                   447    "                                                                                                   ##STR569##                yellow                   448    "                                                                                                   ##STR570##                greenish yellow          449                                                                                    ##STR571##                                                                                         ##STR572##                red                      450                                                                                    ##STR573##                                                                                         ##STR574##                red                      451    "                                                                                                   ##STR575##                red                      __________________________________________________________________________

EXAMPLE 452-457

5-(Phenylcarbamoyl)-2-(5-phenyl-1,3,4-oxdiazolyl)-aniline is prepared analogously to Example 419 from the corresponding 4-phenylcarbamoyl-anthranilic acid and is diazotized and coupled with the coupling components shown in the table. This gives the corresponding dyes, having the hue shown in the table.

    ______________________________________                                         Example No.                                                                             Coupling component      Hue                                           ______________________________________                                         452                                                                                      ##STR576##             red                                           453                                                                                      ##STR577##             red                                           454                                                                                      ##STR578##             red                                           455                                                                                      ##STR579##             yellow                                        456                                                                                      ##STR580##             yellow                                        457                                                                                      ##STR581##             yellow                                        ______________________________________                                    

EXAMPLE 458-462

5-(2,5-Dichlorophenylcarbamoyl)-2-(5-phenyl,3,4-oxdiazolyl)aniline is prepared analogously to Example 419 from the corresponding 4-(2,5-dichlorophenylcarbamoyl)-anthranilic acid and is diazotized and coupled with the coupling components shown in the table. This gives the corresponding dyes, having the hue shown in the table:

    ______________________________________                                         Example No.                                                                             Coupling component      Hue                                           ______________________________________                                         458                                                                                      ##STR582##             red                                           459                                                                                      ##STR583##             red                                           460                                                                                      ##STR584##             red                                           461                                                                                      ##STR585##             yellow                                        462                                                                                      ##STR586##             yellow                                        ______________________________________                                    

The dyes of the formula I characterized, in the table which follows, by R and by the coupling component, are also obtained analogously to Example 301.

    __________________________________________________________________________     Example No.                                                                              R               Coupling component            Hue                    __________________________________________________________________________     463     CH.sub.3                                                                                          ##STR587##                  red                     464     "                                                                                                 ##STR588##                  orange                  465     "                                                                                                 ##STR589##                  yellow                  466     "                                                                                                 ##STR590##                  yellow                  467     CH.sub.2 C.sub.6 H.sub.5                                                                          ##STR591##                  reddish orange          468     "                                                                                                 ##STR592##                  red                     469                                                                                     ##STR593##       "                            bluish red              470                                                                                     ##STR594##       "                            bluish red              471                                                                                     ##STR595##                                                                                       ##STR596##                  bluish red              472                                                                                     ##STR597##                                                                                       ##STR598##                  red                     473                                                                                     ##STR599##                                                                                       ##STR600##                  reddish orange          474                                                                                     ##STR601##                                                                                       ##STR602##                  yellow                  475                                                                                     ##STR603##                                                                                       ##STR604##                  yellow                  476                                                                                     ##STR605##                                                                                       ##STR606##                  reddish brown           477                                                                                     ##STR607##       CH.sub.3 COCH.sub.2 CONHC.sub.6 H.sub.5                                                                     greenish yellow         478                                                                                     ##STR608##                                                                                       ##STR609##                  yellow                  479     "                                                                                                 ##STR610##                  red                     480     "                                                                                                 ##STR611##                  reddish brown           481                                                                                     ##STR612##                                                                                       ##STR613##                  bluish red              482     "                                                                                                 ##STR614##                  yellow                  483                                                                                     ##STR615##                                                                                       ##STR616##                  brown                   484     CONHC.sub.6 H.sub.5                                                                               ##STR617##                  bluish red              485     "                                                                                                 ##STR618##                  bluish red              486     "                                                                                                 ##STR619##                  bluish red              487     "                                                                                                 ##STR620##                  red                     488                                                                                     ##STR621##                                                                                       ##STR622##                  red                     __________________________________________________________________________

Using the diazo components of the formula ##STR623## corresponding dyes are obtained analogously to Example 301:

    __________________________________________________________________________     Example                                                                        No.  R.sup.1       R.sup.2           Hue                                       __________________________________________________________________________     489                                                                                  ##STR624##                                                                                   ##STR625##       orange                                    490                                                                                  ##STR626##                                                                                   ##STR627##       red                                       491                                                                                  ##STR628##                                                                                   ##STR629##       red                                       492                                                                                  ##STR630##                                                                                   ##STR631##       red                                       493                                                                                  ##STR632##                                                                                   ##STR633##       red                                       494                                                                                  ##STR634##                                                                                   ##STR635##       red                                       495                                                                                  ##STR636##                                                                                   ##STR637##       red                                       496                                                                                  ##STR638##                                                                                   ##STR639##       orange                                    497                                                                                  ##STR640##   CONH.sub.2        red                                       498                                                                                  ##STR641##                                                                                   ##STR642##       red                                       499                                                                                  ##STR643##                                                                                   ##STR644##       red                                       500                                                                                  ##STR645##   CONH.sub.2        red                                       501                                                                                  ##STR646##                                                                                   ##STR647##       red                                       502                                                                                  ##STR648##                                                                                   ##STR649##       red                                       __________________________________________________________________________

Analogously to Example 402, the amines shown in the table which follows give the corresponding dyes:

    ______________________________________                                         Example                                                                        No.     Amine                   Hue                                            ______________________________________                                         503                                                                                     ##STR650##             red                                            504                                                                                     ##STR651##             reddish orange                                 505                                                                                     ##STR652##             reddish brown                                  506                                                                                     ##STR653##             red                                            507                                                                                     ##STR654##             red                                            508                                                                                     ##STR655##             red                                            509                                                                                     ##STR656##             orange                                         510                                                                                     ##STR657##             red                                            511                                                                                     ##STR658##             red                                            512                                                                                     ##STR659##             bluish red                                     513                                                                                     ##STR660##             red                                            514                                                                                     ##STR661##             orange                                         515                                                                                     ##STR662##             red                                            516                                                                                     ##STR663##             reddish orange                                 517                                                                                     ##STR664##             red                                            ______________________________________                                    

The following coupling components can also be used analogously to Example 301:

    ______________________________________                                         Ex.                                                                            No.  Coupling component          Hue                                           ______________________________________                                         518                                                                                  ##STR665##                 green- ish yellow                             519                                                                                  ##STR666##                 green- ish yellow                             520                                                                                  ##STR667##                 yellow                                        521                                                                                  ##STR668##                 yellow                                        522                                                                                  ##STR669##                 green- ish yellow                             523                                                                                  ##STR670##                 yellow                                        524                                                                                  ##STR671##                 yellow                                        525                                                                                  ##STR672##                 green- ish yellow                             526                                                                                  ##STR673##                 green- ish yellow                             527                                                                                  ##STR674##                 red                                           528                                                                                  ##STR675##                 red                                           529                                                                                  ##STR676##                 red                                           ______________________________________                                    

Use EXAMPLE 1 In surface coatings

5 Parts of the dye obtained according to Example 2 and 95 parts of a baking finish (eg. 70% of coconut alkyd resin in the form of a 60% strength solution in xylene, and 30% of melamine resin in the form of a solution of about 55% strength in butanol/xylene) are milled in an attrition mill. After applying a coat of the mixture and baking this for 30 minutes at 120° C., brilliant richly colored surface coatings of very good fastness to light and to over-coating are obtained.

Brilliant whitening effects are achieved by addition of, eg., TiO₂.

EXAMPLE 2 In plastics

Deep, light-fast and above all brilliant colorations of plasticized PVC are achieved by working, eg., 0.05 part of the organic pigment obtained according to Example 1 into 50 parts of a plasticized PVC mixture consisting of 65 parts of PVC powder (eg. Vinoflex 531 (a registered tradename)), 35 parts of plasticizer (eg. Palatinol AH (a registered tradename)) and 2 parts of stabilizer. To color the material, it is worked on a heated mixing mill at 140° C. for from 8 to 10 minutes.

Whitened blends are obtainable analogously, eg. by additionally mixing 2.5 parts of TiO₂ (eg. grade RN 56) with 0.25 part of the dye obtained according to Example 1 and 50 parts of a plasticized PVC mixture.

EXAMPLE 3 In printing inks

5 Parts of the dye obtained according to Example 1, from 30 to 40 parts of a resin (eg. rosin modified with a phenol-formaldehyde resin) and from 65 to 55 parts of toluene are thoroughly mixed in a dispersing device. This gives a toluene-based gravure printing ink of excellent fastness to light and outstanding brilliance. 

We claim:
 1. A compound of the formula ##STR677## in which K is ##STR678## Ar¹ is phenyl; phenyl substituted by chlorine, methoxy, ethoxy, methyl, acetylamino or benzoylamino; or ##STR679## Ar² is phenyl; or phenyl substituted by chlorine, methyl or sulfamoyl,T¹ is methyl or carbamoyl, T² is cyano or carbamoyl, Z is hydrogen, chlorine, bromine or trifluoromethyl, Z¹ is hydrogen, chlorine, or bromine, and R is phenyl; phenyl substituted by chlorine, bromine, hydroxy, methoxy, ethoxy, C₁ to C₄ alkyl, cyano, carbamoyl, nitro, phenyl, sulfamoyl, N-phenylsulfamoyl, acetylamino or benzoylamino; naphthyl; N-phenylphthalimidyl; or pyridyl.
 2. A compound as set forth in claim 1 in whichAr² is phenyl or phenyl substituted by chlorine or methyl, T¹ is methyl R is phenyl, phenyl substituted by chlorine, bromine, methyl, nitro or N-phenylphthalimidyl, and K, Ar¹, T², Z and Z₁ have the meanings set forth in claim
 1. 3. A compound as set forth in claim 1 of the formula: ##STR680##
 4. A compound as set forth in claim 1 of the formula: ##STR681##
 5. A compound as set forth in claim 1 of the formula: ##STR682## 